Carbon and mineral transformations in seafloor serpentinization systems

Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution February 2018This thesis examines abiotic processes controlling the transformation and distribution of carbon compounds in seafloor hydrothermal systems hosted in ultramafic rock. These processes have a direct impact on carbon budgets in the oceanic lithosphere and on the sustenance of microorganisms inhabiting hydrothermal vent ecosystems. Where mantle peridotite interacts with carbon-bearing aqueous fluids in the subseafloor, dissolved inorganic carbon can precipitate as carbonate minerals or undergo reduction by H2(aq) to form reduced carbon species. In Chapters 2 and 3, I conduct laboratory experiments to assess the relative extents of carbonate formation and CO2 reduction during alteration of peridotite by CO2(aq)-rich fluids. Results from these experiments reveal that formation of carbonate minerals is favorable on laboratory timescales, even at high H2(aq) concentrations generated by serpentinization reactions. Although CO2(aq) attains rapid metastable equilibrium with formate, formation of thermodynamically stable CH4(aq) is kinetically limited on timescales relevant for active fluid circulation in the subseafloor. It has been proposed that CH4 and potentially longer-chain hydrocarbons may be sourced, instead, from fluid inclusions hosted in plutonic and mantle rocks. Chapter 4 analyzes CH4-rich fluid inclusions in olivine-rich basement rocks from the Von Damm hydrothermal field and the Zambales ophiolite to better understand the origin of abiotic hydrocarbons in ultramaficinfluenced hydrothermal systems. Comparisons of hydrocarbon abundances and stable isotopic compositions in fluid inclusions and associated vent fluids suggest that fluid inclusions may provide a significant contribution of abiotic hydrocarbons to both submarine and continental serpentinization systems.This thesis research was funded by the National Science foundation through grants OCE- 1427274 and OCE-1634032. Louise Von Damm generously contributed financial support for research conducted in Chapter 4

Abiotic methane synthesis and serpentinization in olivine-hosted fluid inclusions

© The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Proceedings of the National Academy of Sciences.of the United States of America 116(36), (2019): 17666-17672. doi:10.1073/pnas.1907871116.The conditions of methane (CH4) formation in olivine-hosted secondary fluid inclusions and their prevalence in peridotite and gabbroic rocks from a wide range of geological settings were assessed using confocal Raman spectroscopy, optical and scanning electron microscopy, electron microprobe analysis, and thermodynamic modeling. Detailed examination of 160 samples from ultraslow- to fast-spreading midocean ridges, subduction zones, and ophiolites revealed that hydrogen (H2) and CH4 formation linked to serpentinization within olivine-hosted secondary fluid inclusions is a widespread process. Fluid inclusion contents are dominated by serpentine, brucite, and magnetite, as well as CH4(g) and H2(g) in varying proportions, consistent with serpentinization under strongly reducing, closed-system conditions. Thermodynamic constraints indicate that aqueous fluids entering the upper mantle or lower oceanic crust are trapped in olivine as secondary fluid inclusions at temperatures higher than ∼400 °C. When temperatures decrease below ∼340 °C, serpentinization of olivine lining the walls of the fluid inclusions leads to a near-quantitative consumption of trapped liquid H2O. The generation of molecular H2 through precipitation of Fe(III)-rich daughter minerals results in conditions that are conducive to the reduction of inorganic carbon and the formation of CH4. Once formed, CH4(g) and H2(g) can be stored over geological timescales until extracted by dissolution or fracturing of the olivine host. Fluid inclusions represent a widespread and significant source of abiotic CH4 and H2 in submarine and subaerial vent systems on Earth, and possibly elsewhere in the solar system.We are indebted to J. Eckert for his support with FE-EMPA; to K. Aquinho and E. Codillo for providing samples from Zambales; to K. Aquinho for Raman analysis of some of the samples from Zambales and Mt. Dent; to H. Dick for providing access to his thin section collection; to the curators of the IODP core repositories for providing access to Ocean Drilling Program (ODP) and Integrated Ocean Drilling Program (IODP) samples; and to the captains and crews of the many cruises without whom the collection of these samples would not have been possible. Reviews by Peter Kelemen and an anonymous referee greatly improved this manuscript. This study is supported with funds provided by the National Science Foundation (NSF-OCE Award 1634032 to F.K. and J.S.S.).2020-02-1

Chemical and isotopic analyses of hydrocarbon-bearing fluid inclusions in olivine-rich rocks

We examined the mineralogical, chemical and isotopic compositions of secondary fluid inclusions in olivine-rich rocks from two active serpentinization systems: the Von Damm hydrothermal field (Mid-Cayman Rise) and the Zambales ophiolite (Philippines). Peridotite, troctolite and gabbroic rocks in these systems contain abundant CH4-rich secondary inclusions in olivine, with less abundant inclusions in plagioclase and clinopyroxene. Olivine-hosted secondary inclusions are chiefly composed of CH4 and minor H2, in addition to secondary minerals including serpentine, brucite, magnetite and carbonates. Secondary inclusions in plagioclase are dominated by CH4 with variable amounts of H2 and H2O, while those in clinopyroxene contain only CH4. We determined hydrocarbon abundances and stable carbon isotope compositions by crushing whole rocks and analysing the released volatiles using isotope ratio monitoring—gas chromatography mass spectrometry. Bulk rock gas analyses yielded appreciable quantities of CH4 and C2H6 in samples from Cayman (4–313 nmol g−1 CH4 and 0.02–0.99 nmol g−1 C2H6), with lesser amounts in samples from Zambales (2–37 nmol g−1 CH4 and 0.004–0.082 nmol g−1 C2H6). Mafic and ultramafic rocks at Cayman exhibit δ13CCH4 values of −16.7‰ to −4.4‰ and δ13CC2H6 values of −20.3‰ to +0.7‰. Ultramafic rocks from Zambales exhibit δ13CCH4 values of −12.4‰ to −2.8‰ and δ13CC2H6 values of −1.2‰ to −0.9‰. Similarities in the carbon isotopic compositions of CH4 and C2H6 in plutonic rocks, Von Damm hydrothermal fluids, and Zambales gas seeps suggest that leaching of fluid inclusions may provide a significant contribution of abiotic hydrocarbons to deep-sea vent fluids and ophiolite-hosted gas seeps. Isotopic compositions of CH4 and C2H6 from a variety of hydrothermal fields hosted in olivine-rich rocks that are similar to those in Von Damm vent fluids further support the idea that a significant portion of abiotic hydrocarbons in ultramafic-influenced vent fluids is derived from fluid inclusions

Experimental constraints on fluid-rock reactions during incipient serpentinization of harzburgite

Author Posting. © The Author(s), 2014. This is the author's version of the work. It is posted here by permission of Mineralogical Society of America for personal use, not for redistribution. The definitive version was published in American Mineralogist 100 (2015): 991-1002, doi:10.2138/am-2015-5112.The exposure of mantle peridotite to water at crustal levels leads to a cascade of interconnected dissolution-precipitation and reduction-oxidation reactions—a process referred to as serpentinization. These reactions have major implications for microbial life through the provision of hydrogen (H2). To simulate incipient serpentinization under well-constrained conditions, we reacted centimeter-sized pieces of uncrushed harzburgite with chemically modified seawater at 300 ºC and 35 MPa for ca. 1.5 yr (13 441 h), monitored changes in fluid chemistry over time, and examined the secondary mineralogy at the termination of the experiment. Approximately 4 mol% of the protolith underwent alteration forming serpentine, accessory magnetite, chlorite, and traces of calcite and heazlewoodite. Alteration textures bear remarkable similarities to those found in partially serpentinized abyssal peridotites. Neither brucite nor talc precipitated during the experiment. Given that the starting material contained ~4 times more olivine than orthopyroxene on a molar basis, mass balance requires that dissolution of orthopyroxene was significantly faster than dissolution of olivine. Coupled mass transfer of dissolved Si, Mg, and H+ between olivine and orthopyroxene reaction fronts was driven by steep activity gradients and facilitated the precipitation of serpentine. Hydrogen was released in significant amounts throughout the entire experiment; however, the H2 release rate decreased with time. Serpentinization consumed water but did not release significant amounts of dissolved species (other than H2) suggesting that incipient hydration reactions involved a volume increase of ~40%. The reduced access of water to fresh olivine surfaces due to filling of fractures and coating of primary minerals with alteration products led to decreased rates of serpentinization and H2 release. While this concept might seem at odds with completely serpentinized seafloor peridotites, reaction-driven fracturing offers an intriguing solution to the seemingly self-limiting nature of serpentinization. Indeed, the reacted sample revealed several textural features diagnostic of incipient reaction-driven fracturing. We conclude that fracturing must have far reaching impacts on the rates of serpentinization and H2 release in peridotite-hosted hydrothermal systems.This study was partially supported by the National Science Foundation (NSF-OCE grants 1059534 to F.K. and S.E.H. and OCE-0927744 To T.M.M.) and the Deep Ocean Exploration Institute at the Woods Hole Oceanographic Institution.2016-04-0